Vat dyestuffs



United States Patent "ice VAT DYESTUFFS Jacob Koch, Basel, and Walter Kern, Sissach, Switzerland, giggnorsto Ciba Limited, Basel, Switzerland, a Swiss N.) Drawing. Application July 17, 1950, Serial No. 174,361

Claims priority, application Switzerland July 21, 1949 8 laims. (Cl. 260-276) This invention is based on the observation that dicarbazoles obtainable from trianthrimides of the general formula in which R1 and R2 each represent an anthraquinone radical bound to the imino group in the l-position and at least one of which radicals contains an acridone ring fused on the 3:4-position are valuable vat dyestuffs.

The trianthrimides of the above general formula may be made, for example, by condensing one molecular proportion of a 1:8-dihalogen-anthraquinone, advantageously 1:8-dichloranthraquinone, with two molecular proportions of a 4-amino-anthraquinone-2:l(N)-1:2(N)-benzacridone or in succession or simultaneously with one molecular proportion of such an anthraquinone-acridone and one molecular proportion of any desired l-aminoanthraquinone. As the latter component it is of advantage to choose an aminoanthraquinone-acridone different from that constituting the first component or a laminoanthraquinone which contains in a further u-position an acylamino group, advantageously a benzoylamino group, for example, l-amino-4-, 5- or 8-benzoylaminoanthraquinone, in which case the benzoyl radical may contain substituents, especially of non-ionogenic character and of a molecular weight not exceeding about 130, such as halogen atoms, alkoxy groups, alkylsulfone groups and dialkyl sulfamide groups. The reaction may be carried out in a high boiling solvent which does not react with the starting materials, for example, in naphthalene or nitrobenzene, advantageously in the presence of one of the usual catalysts which promote anthrimide formation, such as copper or a copper salt and if desired with the addition of an acid-binding agent. As examples of. such trianthrimides there may be mentioned products which are obtained by the reaction of one molecular proportion of l:8-dichloranthraquinone with two molecular proportions of a 4-aminoanthraquinone-2: l(N)-1' :2(N)- benzacridone, or from one molecular proportion of 1:8- dichloranthraquinone. one molecular proportion of 4- aminoanthraquinone-2: l (N) l 2' (N benzacridone and one molecular proportion of 1-amino-4-, 5- or 8-benzoylaminoanthraquinone, and also analogous products, especially those of asymmetrical character, in which the B2- nucleus of the benzacridone ring contains halogen as a substituent.

As carba-zolizing agents for treating the above mentioned trianthrimides in accordance with the present process there come into consideration, for example, titanium tetrachloride and especially aluminium chloride. The reaction may be carried out in a manner in itself known in the presence of a suitable solvent or diluent, for example, in the presence of a tertiary base such as pyridine, but advantageously in the presence of nitrobenzene or with the aid of the known addition products of sulfur dioxide and aluminium chloride.

2,695,296 Patented Nov. 23, 1954 NH NH O I wherein R1 and R2 stand for an anthraquinone radical bound in l-position to the NH- group and wherein an acridone ring is fused on to at least one of the radicals R1 and R2 in its positions 3 and 4. They are valuable vat dyestuifs which are distinguished especially by good fastness to light and also by good properties of fastness in general. They may be used as pigment dyestuifs, or for dyeing or printing a very wide variety of fibers such as wool, silk and especially vegetable, fibers such as cotton, linen, artificial silk and staple fibers of regenerated cellulose, and if desired they may be used in the form of their leuco-ester salts obtainable in known manner for dyeing or printing by the methods known for this class of dyestuffs.

The following examples illustrate the invention, the parts and percentages being by weight:

EXAMPLE 1 A. Preparation of the trianthrimide.-In a finely pul- Verizedstate 11.1 parts of l:8-dichloranthraquinone, 28.6 parts of 4-arninoanthraquinone-2:l(N)-1:2(N)-benzacridone, 8 parts of anhydrous sodium acetate, 4. parts of magnesium oxide and 2 parts of cuprous chloride are mixed with 200 parts of naphthalene. The mixture is heated, and the melt is stirred While gently boiling until the starting materials have disappeared. The whole is then allowed to cool to 160 C., diluted with 200 parts of monochlorobenzene, and stirred for one hour at 140- 150 C. After cooling to about 90 C., the whole is filtered with suction. The filter residue is purified by treatment in turn with mono-chlorobenzene, alcohol, dilute hydrochloric acid and finally water, and then dried. The yield amounts to 90-95% of the theoretical yield. The dyestuflf of the formula NH (I? NH 11TH m GOD is a greenish-blue powder which dissolves in concentrated sulfuric acid with a brownish yellow coloration and dyes cotton from a violet-brown vat grey tints having very good properties of fastness.

B. Carbazolization, first variant-12 parts of the trianthrimide obtained as described in paragraph A above are introduced in the course of hour at about -90 C. into a thinly fluid homogeneous melt which has been obtained from a mixture of 84 parts of sublimed aluminium chloride and 16.8 parts of dry powdered sodium chloride by passing dry sulfur dioxide gas through the mixture. The whole is stirred for a further hour at 100 C. while continuing to pass sulfur dioxide through the mixture. The fluid melt is then stirred into a mixture of 1500 parts of water and 400 parts of caustic soda solution of 36 B. The suspension which has become warm, is stirred for one hour at 70 C., and then filtered with suction. The washed residue is added to a mixture of 375 parts of Water and parts of sulfuric monohydrate. The suspension is stirred for one hour at 70 C., and then filtered with suction. The residue is washed until neutral and dried. The dyestufi so obtained is a dark powder of the formula which dissolves in concentrated sulfuric acid with a blue coloration. It dyes cotton from an orange-brown vat blackish olive-brown tints having remarkable properties of fastness.

C. Carbazolization, second varianz.44.5 parts of sublimed aluminium chloride are strewn into 89 parts of nitrobenzene while stirring, whereupon the temperature of the resulting solution rises to about 70 C. The whole is allowed to cool to about 50 C., and then 8.9 parts of the trianthrirnide obtained as described in paragraph A above are introduced in the course of A hour. The whole is heated to 85 C., and stirred for one hour at 8590 C. After cooling to room temperature, the thin melt is introduced into a mixture of 200 parts of water and 270 parts of caustic soda solution of 36 B., and the nitrobenzene is removed by steam distillation. The suspension which remains behind is filtered with suction, and the filter residue is washed until neutral and dried. The dyestulf so obtained is identical with that described in paragraph B above.

EXAMPLE 2 The procedure is the same as that described in Example 1 except that, instead of 4-aminoanthraquinone-2:1(N)- 1:2'(N)-benzacridone, derivatives thereof chlorinated in the Bznucleus are used. Analgous dyestuffs are obtained. The properties of a few of these dyestufis are given in the following tables, the first table relating to the trianthrimides and the second to the dicarbazoles.

Trianthrz'mides Dicarbazoles Dyestutf Coloration Aeridone compound 5 2 2 2 3 Color of Tint of dyeing Hated vat on cotton 4 aminoanthraquinone-2zl Red-blue. Brown" Brownish olive.

(N) -112 (N) -5' chlorobenzacridone. 4 aminoanthraquinone-2d Blue-grey do Slate grey.

(N)-l' :2 (N)-6 chlorobenzacridone. 4 aminoanthraquinone-2z1 Violet do Greenish olive.

(N) -1' :2 (N) -3 :5 dichloro benzacridone.

EXAMPLE 3 A. Preparation of the trianthrimidcQ-Jn a finely powdered condition 13.8 parts of 1:8-dichloranthraquinone, 17 parts of 4-aminoanthraquinone-2:1(N)- 1':2(N)-benzacridone, 5 parts of anhydrous sodium acetate, 2.5 parts of magnesium oxide and 1.5 parts of cuprous chloride are added to parts of nitrobenzene. The whole is heated and stirred at a gentle boil until the starting products have disappeared. After cooling to about 90 C. the whole is filtered with suction. The filter residue is purified by treatment with alcohol, dilute hydrochloric acid and water, and then dried. The yield amounts to 85-90 per cent of the theoretical yield. The compound is a dark greenish blue powder which dissolves in concentrated sulfuric acid with a brown-yellow coloration.

In a finely powdered condition 17.45 parts of the product so obtained, 10.8 parts of l-amino-4-benzoylaminoanthraquinone, 3' parts of anhydrous sodium acetate, 1.5 parts of magnesium oxide and 1 part of cuprous chloride are mixed with parts of naphthalene. The whole is heated and the melt is stirred at a gentle boil until the starting products have disappeared. The whole is then allowed to cool to about C., diluted with monochlorobenzene, and worked up as described in paragraph A of Example 1. The yield amounts to 80-90 per cent of the theoretical yield. The compound so obtained is a dark blue powder of the formula which dissolves in concentrated sulfuric acid with a yellowish olive green coloration and dyes cotton from an orange-brown vat grey tints having very good properties of fastness.

B. Carbazolization.--The trianthrimide obtained as described in the preceding paragraph is treated as described in paragraph B or C of Example 1, and there is obtained a dyestutf which dissolves in concentrated sulfuric acid with a violet coloration. It dies cotton from an orange-brown vat yellowish brown tints having remarkable properties of fastness.

EXAMPLE 4 By using the first paragraph of Example 3 a derivative of 4-aminoanthraquinone-2: 1 (N) 1 2' (N) -benzacridone chlorinated in the benzene nucleus and/ or in accordance with the second paragraph of the same example another 1-amino-a-acylaminoanthraquinone, instead of l-amino- 4-benzoylaminoanthraquinone, analogous dyestuffs are obtained. The properties of a number of such dyestuffs are given in the following tables, the first table relating to 1the trianthrimides and the second table to the dicarbazo es: v t

- Trianthrimides ii v i i I 1 7 i A 7 v 1 Outer components Dyestufi I Acridone compound Amino-acylamino-anthraquinone gggfiggfi gg gz a Color of vat: 8; gagg 4- aminoanthraquinone 2:1(N) 1 :2(N) I-aminoi-(paramethylsulfonyD-ben- Yellowi'sh olive green... Red-brown. 5 Grey.

benzacridone. zoylamino-anthraquinones Do 1-amino-4-(para-[N-dimethyH-suldo Do.

fonamido) benzoylamino anthra 5 qumone. t Do l-ainino-5-benzoy1amino-anthraquin- Orange brown. Violetish grey.

one. Do 1-amino-S-benzoylamino-anthraquindo Do.

one. 4-an1inoanthraquinone-2:1(N)-1:2(N)-5'- l-aniino-S-benzoylamino-anthraquin- Bordeaux Violetish brown.

chlorobenzacridone. one. 4-arninoanthraquinone-2:1(N)-1:2(N)- do Orange brown- Grey.

Mohtorobenzaeridone. 4-aminoanthraqninone-2:1(N) -1:2'(N) do Bordeauxfinn Redd i'sh' black- 3:5dich1orobenzacrldone. brown.

Dicarbazoles Outer components Dyestufi Acridone compound Amino-aeylamino-anthraquinonc g gfizggg ffgga Color ot vat gggg g 4-aminoanthraquinone-2:1(N)-1':'(N)-benzl-amino-4-('paramethylsulfonyl)- Red-brown..." Yellowish brown.

acridone. benzoylamino-anthraquinene. p D l-aminoi-(para-[N-dirnethyl]-sulfon 0range-brown Do.

amido-benzoylamino-anthraquinone. D0 l-amino-5-benzoyl amino-anthraquinone. .d0 D0. D0 1-amino-8-benzoy1-amino-anthraquinone. Yellow-brown. Black-brown. 4-aminoanthraquinone- (N )-1:2(N)-5- l-amine-5-benzoy1-aminoanthraquinone. ,Brown Yellowish brown.

ohlorobenzaeridone. 4-aminoanthraquinone-2z1(N)-1:2'(N)-6- do Orange-brown. Do.

chlorobenzacridone. 4-aminoanthraquinone-2z1(N)-1:2'(N)'3 :5- dn Brown D0.

diehlorobenzacridone. 7

EXAMPLE 5 EXAMPLE 6 By reacting the dianthrirnide obtainable as described in the first paragraph of Example 3 with S-am-inoor 8- amino-anthraquinone-Z: 1 (N) 1' 2 (N) -benzacridone, in-

stead of 1-amino-4-benzoy1arninoanthraquinone, in the manner described in the second paragraph of that example, there are also obtained; asymmetrical trianthrimides.

1.5 parts of the vat dyestufi? obtained as described in paragraph B or C of Example 1 are vatted in 6 parts by volume of caustic soda solution of 36 B. and 3 parts of sodium hydrosulfite at about 50 C. in 300 parts of water. This stock vat is added to a dyebath containing, in 1700 parts of Water, 4 parts by volume of caustic soda solution of 36 B. and 2 parts of sodium hydrosulfite, and 100 parts of cotton are entered at 40 C. After minutes parts of sodium chloride are added, and dyeing is carried on at 50 C. for one hour. The cotton is then squeezed, oxidised in the air, rinsed, acidified and again rinsed, and if desired soaped at the Trianthrimia'es Dyestufi 7 Colora- First aeridone-component Second aeridone component gfifi gg in Color of vat ggfi concentra'ted 1 H2504 4-andrinoanthraquinone-zzl(N)-1:2(N)-benzac- 5-aminoanthraquinone-2z1(N)-1:2-(N)-benzacridone. Orange.. Bordeaux..- Blaekish-violet.

r1 one.

Do S-amimanthraquinone-Zzl(N)-1:2-(N)-benzacridone do do Bluish grey.

" v Dicarbazoles Dyestufl! Qolora- First aeridone component Second acridone component g fi gg in Color of vat 3; gggg concentrated H2804 4-arrd1inoanthraquinone-2:1(N)-1':2(N)-benzacfi-aminoanthraquinone-Z:1(N)-1:2'-(N)-benzaeridone Violet Red-brown- Vigletish black- 11 one. rown.

Do B-aminoanthraquinone-Z:1(N)-1:2'-(N)-benzaeridone.. .do do Blackish brown.

1. An anthraquinone vat dyestufi of the formula 2,695,296 18 boil. The cotton is dyed a fast blackish-olive brown wherein R1 and R2 each stands for mononuclear carbotint. cyclic aryl.

What we claim is: 3. An anthraquinone vat dyestufi of the formula EN NE 0 HNR2 n1 co wherein R1 stands for mononuclear carbocyclic aryl, and

R2 stands for anthraquinonyl containing one 9: IO-dioxoanthracene nucleus and bound to the adjacent -NH group in an wposition. for mononuclear carbocychc aryl.

2. An anthraquinone vat dyestufi of the formula The dyesmfi of the formula O O O 0- O NH HN NH 0 EN NH O C B: C O O C wherein R1 stands for mononuclear carbocyclic aryl, two Xs represent hydrogen atoms and one X represents a 20 group of the formula NHCO-R3 in which R3 stands 5. The dyestuff of the formula 9 8. The dyestufi of the formula References Cited in the file of this patent N mbe 65 2,212,9 UNITED STATES PATENTS 2,315,537 Number Name Date 1781,22 Mi g gov. 339

,878,9 Mieg ept.

1,969,210 Dettwyler et a1 Aug. 7, 1934 5 1 1 2 2,036,663 Weiland er. a1. Apr. 7, 1936 719345 Name Date Weiners Aug. 27, 1940 Miller Apr. 6, 1943 FOREIGN PATENTS Country Date Switzerland Dec. 2, 1940 Germany Apr. 11, 1942 

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE FORMULA 